Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/024—Emulsion paints including aerosols characterised by the additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09G—POLISHING COMPOSITIONS; SKI WAXES
  • C09G1/00—Polishing compositions
  • C09G1/06—Other polishing compositions
  • C09G1/14—Other polishing compositions based on non-waxy substances
  • C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C3/00—Tanning; Compositions for tanning
  • C14C3/02—Chemical tanning
  • C14C3/08—Chemical tanning by organic agents
  • C14C3/22—Chemical tanning by organic agents using polymerisation products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/66—Substances characterised by their function in the composition

Definitions

• compositions contain at least one polymer dispersed in water and at least one polyvalent metal cation.
• the polymer has acid functionality.
• Such compositions are useful for a variety of purposes, for example as ingredients in leather treatments and floor polishes.
• many known examples of such compositions had relatively low level of polyvalent cation, though, in some cases, the usefulness of such a composition is improved if the composition has a higher level of polyvalent metal cation.
• Higher levels of polyvalent cation are considered to improve the properties of such compositions; for example, coatings such as, for example, floor polishes, are thought to be more durable if higher levels of polyvalent metal cation are used.
• composition comprising
• (meth)acrylate and “(meth)acrylic” mean, respectively, “acrylate or methacrylate” and “acrylic or methacrylic.”
• a material is "aqueous" if that material contains at least 25% water by weight, based on the total weight of that material.
• a "dispersion" contains, sometimes among other ingredients, discrete particles that are suspended in a continuous medium.
• the continuous medium contains at least 50% water by weight, based on the weight of the continuous medium, the dispersion is said to be an "aqueous dispersion," and the continuous medium is said to be an "aqueous medium.”
• the dispersion is said herein to be a "polymer dispersion.”
• an "aqueous polymer dispersion" contains some polymer-containing particles suspended in a continuous medium that is at least 50% water.
• the group of polymer particles in a sample of an aqueous polymer dispersion have a variety of sizes.
• the polymer particles are spherical or nearly spherical; in such cases their sizes can usefully be characterized by their diameters, and the group of polymer particles can be usefully characterized by the average diameter of the particles.
• One useful method of measuring the average diameter of the particles is light scattering.
• the average diameter of the particles is 80 nm or larger; or 100 nm or larger; or 125 nm or larger.
• the average diameter of the particles is 1,000 nm or smaller; or 500 nm or smaller; or 250 nm or smaller.
• the average diameter of the particles is smaller than 150 nm.
• the polymer of the aqueous polymer dispersion of the present invention is formed by the polymerization of monomers; the aggregate of all monomers used to form the polymer is known herein as the "monomer mix.”
• Monomers in the monomer mix may be of any type and may polymerized by any method or mechanism.
• the monomer mix contains 5% or more by weight of one or more carboxylic acid functional monomers, based on the weight of the monomer mix. In some embodiments, the monomer mix contains 7% or more; or 9% or more, by weight of one or more carboxylic acid functional monomers, based on the weight of the monomer mix. In the practice of the present invention, the monomer mix contains 50% or less by weight of one or more carboxylic acid functional monomers, based on the weight of the monomer mix. In some embodiments of the present invention, the monomer mix contains 20% or less by weight of one or more carboxylic acid functional monomers, based on the weight of the monomer mix. In some embodiments, the monomer mix contains 15% or less; or 12% or less, by weight of one or more carboxylic acid functional monomers, based on the weight of the monomer mix.
• Carboxylic acid functional monomers are compounds capable of polymerization that contain at least one carboxylic acid group.
• the carboxylic acid group may be in the form of a neutral carboxylic acid group, in the form of a carboxylate ion, or in any mixture or combination thereof.
• carboxylic acid functional monomers are used that have carboxylic acid functional groups, and the carboxylic acid functional groups are not removed or altered during the process of polymerization.
• monomers with other functional groups that, after polymerization, are converted to carboxylic acid functional groups.
• the monomer mix of the present invention contains monomers other than carboxylic acid functional monomers, known herein as "non-carboxyl monomers.”
• the non-carboxyl monomer or monomers may be of any type that is capable of forming a copolymer with the carboxylic acid functional monomers that are used.
• Copolymer refers to a polymer made from two or more different monomers that react together to form a polymer. Copolymers may have any structure; for example, the different monomers may be arranged randomly, in a pattern (such as, for example, alternation), in blocks, in branches, in a star, or in any combination thereof.
• some or all of the monomers in the monomer mix are vinyl monomers (i.e., monomers that each contain at least one vinyl group).
• carboxylic acid functional vinyl monomers are, for example, vinyl compounds with at least one carboxylic acid functional group, such as, for example, alpha, beta monoethylenically unsaturated acids; partial esters of unsaturated aliphatic dicarboxylic acids and the alkyl half esters of such acids; and mixtures thereof.
• carboxylic acid functional vinyl monomers are, for example, vinyl compounds with at least one carboxylic acid functional group, such as, for example, alpha, beta monoethylenically unsaturated acids; partial esters of unsaturated aliphatic dicarboxylic acids and the alkyl half esters of such acids; and mixtures thereof.
• Some suitable alpha, beta monoethylenically unsaturated acids are, for example, maleic acid, fumaric acid, aconitic acid, crotonic acid, citraconic acid, acryloxypropionic acid, acrylic acid, methacrylic acid (MAA), itaconic acid, and mixtures thereof.
• MAA is known
• alkyl half esters of unsaturated aliphatic dicarboxylic acids are, for example, the alkyl half esters of itaconic acid, fumaric acid and maleic acid.
• suitable alkyl groups for such alkyl half esters are, for example, alkyl groups with 1 to 6 carbon atoms.
• Some examples of such alkyl half esters are methyl acid itaconate, butyl acid itaconate, ethyl acid fumarate, butyl acid fumarate, methyl acid maleate, and mixtures thereof.
• non-carboxyl vinyl monomers are, for example, vinyl aromatic monomers; alkyl esters of (meth)acrylic acid; nonionogenic vinyl monomers that are polar or polarizable; esters of hydroxy vinyl moieties with carboxylic acids; other non-carboxyl ethylenically unsaturated compounds; and mixtures thereof.
• Some suitable vinyl aromatic monomers are, for example, alpha, beta monoethylenically unsaturated aromatic monomers.
• Some suitable alpha, beta monoethylenically unsaturated aromatic monomers are, for example, styrene (Sty), vinyl toluene, 2-bromo styrene, o-bromo styrene, p-chloro styrene, o-methoxy styrene, p-methoxy styrene, allyl phenyl ether, allyl tolyl ether, alphamethyl styrene, and mixtures thereof.
• Styrene is known to be a suitable vinyl aromatic monomer.
• the monomer mix contains at least one vinyl aromatic monomer, in an amount by weight, based on the weight of the monomer mix, of 15% or more, or 25% or more. Independently, in some embodiments, the monomer mix contains at least one vinyl aromatic monomer, in an amount by weight, based on the weight of the monomer mix, of 55% or less, or 45% or less.
• alkyl esters of (meth)acrylic acid are, for example, those in which the alkyl group has 20 or fewer carbon atoms, or 12 or fewer carbon atoms, or 8 or fewer carbon atoms.
• the alkyl group in suitable alkyl esters of (meth)acrylic acid may be linear, branched, cyclic, or any combination or mixture thereof.
• Suitable alkyl esters of (meth)acrylic acid are methyl methacrylate (MMA), methyl acrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate (BA), butyl methacrylate (BMA), iso-butyl methacrylate (IBMA), 2-ethylhexyl acrylate, n-octyl acrylate, sec-butyl acrylate, cyclopropyl methacrylate, isobornyl methacrylate, and mixtures thereof.
• the monomer mix contains BA, MMA, or a mixture thereof.
• the monomer mix contains at least one alkyl acrylate, in an amount by weight, based on the weight of the monomer mix, of 10% or more, or 20% or more. In some embodiments, the monomer mix contains at least one alkyl acrylate, in an amount by weight, based on the weight of the monomer mix, of 60% or less, or 50% or less.
• the monomer mix contains at least one alkyl methacrylate, in an amount by weight, based on the weight of the monomer mix, of 4% or more, or 8% or more. In some embodiments, the monomer mix contains at least one alkyl methacrylate, in an amount by weight, based on the weight of the monomer mix, of 45% or less, or 35% or less.
• the monomer mix contains at least one nonionogenic vinyl monomer that is polar or polarizable.
• Some examples of such monomers are acrylonitrile, methacrylonitrile, cis- and trans- crotononitrile, alpha-cyanostyrene, alpha-chloroacrylonitrile, ethyl vinyl ether, isopropyl vinyl ether, isobutyl- and butyl- vinyl ether, diethylene glycol vinyl ether, decyl vinyl ether, vinyl acetate, hydroxyalkyl (meth) acrylates such as 2-hydroxy ethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxy propyl methacrylate, butanediol acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and mixtures thereof.
• nonionogenic vinyl monomers that are polar or polarizable are those that contain sulfur.
• sulfur-containing nonionogenic vinyl monomers that are polar or polarizable are vinyl thiols such as, for example, 2-mercaptopropyl methacrylate, 2-sulphoethyl methacrylate, methyl vinyl thiol ether, and propyl vinyl thiol ether.
• the monomer mix contains one or more sulfur-containing nonionogenic vinyl monomers that are polar or polarizable. In other embodiments, the monomer mix contains no sulfur-containing nonionogenic vinyl monomers that are polar or polarizable.
• nonionogenic vinyl monomers that are polar or polarizable are ethylenically unsaturated monomers that contain at least one acetoacetate or acetoacetamide grouping.
• the monomer mix includes one or more monomers that contain at least one acetoacetate or acetoacetamide grouping.
• the monomer mix excludes monomers that contain at least one acetoacetate or acetoacetamide grouping.
• the monomer mix contains at least one ester of a hydroxy vinyl moiety with a carboxylic acid.
• the carboxylic acid portion of such an ester is selected from the aromatic and aliphatic carboxylic acids. Suitable aliphatic carboxylic acids include, for example, those with 1 to 18 carbon atoms.
• Such aliphatic carboxylic acids include, for example, formic, acetic, propionic, n-butyric, n-valeric, palmitic, stearic, phenyl acetic, benzoic, chloroacetic, dichloroacetic, gamma-chloro butyric, 4-chlorobenzoic, 2,5-dimethyl benzoic, o-toluic, 2,4,5-trimethoxy benzoic, cyclobutane carboxylic, cyclohexane carboxylic, 1-(p-methoxy phenyl)cyclohexane carboxylic, 1-(p-tolyl)-1-cyclopentane carboxylic, hexanoic, myristic, and p-toluic acids.
• the hydroxy vinyl moiety of such an ester may be, for example, selected from hydroxy vinyl compounds such as hydroxy ethylene, 3-hydroxy-pent-1-ene, 3,4-dihydroxybut-1-ene
• the monomer mix contains one or more monomers with at least one sulfur-containing acid functional group.
• Sulfur-containing acid functional groups include sulfate and sulfonate groups.
• the monomer mix contains no monomers with sulfate groups or sulfonate groups.
• the monomer mix includes no monomers with any sulfur-containing acid functional group.
• the monomer mix includes no monomers that contain sulfur.
• An aqueous polymer dispersion of the present invention may be made by any of a wide variety of methods.
• the polymer may be formed by any polymerization method and then dispersed in water.
• the polymer is formed as suspended particles in an aqueous medium, for example, by suspension polymerization, emulsion polymerization, microemulsion polymerization, or a combination thereof.
• the polymer is formed by emulsion polymerization.
• emulsion polymerization The practice of emulsion polymerization is discussed in detail in D. C. Blackley, Emulsion Polymerization (Wiley, 1975).
• the monomers may be emulsified with anionic or nonionic dispersing agents; about 0.5% to 10% thereof on the weight of total monomers being used.
• a polymerization initiator of the free radical type such as, for example, ammonium or potassium persulphate, may be used alone or in conjunction with an accelerator, such as, for example, potassium metabisulphate or sodium thiosulphate.
• the initiator and accelerator (if used), commonly referred to as catalysts, may conveniently be used in proportions of 0.5% to 2% each based on the weight of monomers to be copolymerized.
• the polymerization temperature may for example be from room temperature to 90°C, or more, as is conventional.
• emulsifiers which are suited to the polymerization process useful in this invention include, for example, alkaline metal and ammonium salts of alkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl sulphonates, sulphates and polyether sulphates, such as sodium vinyl sulphonate, and sodium methallyl sulphonate; the corresponding phosphates and phosphonates, such as phosphoethyl methacrylate; and alkoxylated fatty acids, esters, alcohols, amines, amides and alkylphenols.
• Chain transfer agents including, for example, mercaptans, polymercaptans and polyhalogen compounds, are sometimes used in the polymerization mixture to control polymer molecular weight.
• any of the various types of emulsion polymerization may be used.
• a "single stage" emulsion polymerization is used, in which the monomer mix, sometimes in emulsified form, is either added all at once to the reaction container or is added gradually to the reaction container during the polymerization reaction.
• a "multi-stage" emulsion polymerization in which the monomer mix is provided as two or more portions of different compositions; after each portion is polymerized, all or part of the resulting polymer is kept in or is placed into a vessel, and a subsequent portion of monomer mix is added to that vessel and polymerized.
• monomer mix is contemplated herein to mean the aggregate of all monomers used to make the polymer of the present invention, regardless of the physical form in which the monomer mix is used.
• the monomer mix is provided as a single physical mixture in a single container.
• the monomer mix is provided as two or more mixtures (which may be the same as each other or may be different from each other) of monomers in two or more different containers.
• MFT minimum film formation temperature
• the practice of the present invention involves the use of at least one polyvalent metal cation, which means herein a metal cation with charge of +2 or higher.
• Suitable polyvalent metal cations are, for example, polyvalent cations of alkaline earth metals and polyvalent cations of transition metals.
• suitable metals whose polyvalent cations are suitable for use in the present invention are, for example, magnesium, arsenic, mercury, cobalt, iron, copper, lead, cadmium, nickel, chromium, aluminum, tungsten, tin, zinc, zirconium, and mixtures thereof.
• one or more of zinc, copper, magnesium, and mixtures thereof are used.
• zinc is used.
• magnesium is used.
• At least one polyvalent metal ion is used in the form of a complex.
• suitable complexes include, for example, carbonates, bicarbonates, and glycinates.
• One method to solubilize such a complex is to add the complex to dilute aqueous ammonia; the result is named by inserting "ammonia" into the name of the original complex.
• solubilized complexes are zinc ammonia glycinate and zinc ammonia bicarbonate.
• the polyvalent metal cation prior to its addition to the composition, is in the form of an insoluble metal compound.
• insoluble means a compound that has solubility in water of less than 4.2 g of compound in 100 g of water.
• Suitable insoluble metal compounds include, for example, oxides, hydroxides, carbonates, acetates, and mixtures thereof.
• One suitable insoluble metal compound is zinc oxide.
• the amount of polyvalent metal cation in the composition of the present invention is characterized by the number of equivalents.
• the number of equivalents of that polyvalent metal cation is the number of moles of the cation that is present, multiplied by the valency of the cation.
• One mole of divalent metal cations provides two equivalents; one mole of trivalent metal cations provides three equivalents; and so on.
• the ratio of the equivalents of polyvalent metal cations present in the composition to the equivalents of carboxyl groups is 0.4 or higher. In some embodiments, that ratio is 0.6 or higher; or 0.7 or higher; or 0.8 or higher. Independently, in some embodiments, that ratio is 1.2 or lower; or 1.0 or lower; or 0.9 or lower.
• swelling agent is a compound that interacts with a polymer in a way that increases the flexibility of that polymer.
• the swelling agent is an organic compound.
• the swelling agent is a non-polymeric compound.
• the swelling agent is a non-polymeric organic compound.
• a compound of interest suitable as a swelling agent for a particular aqueous polymer dispersion is to perform a zinc uptake test, as described in the Examples herein below, with that aqueous polymer dispersion and the compound of interest.
• a compound of interest that results in a detectable decrease in zinc precipitate is a suitable swelling agent.
• An alternative method of testing whether a compound of interest is suitable as a swelling agent for a particular aqueous polymer dispersion is to measure the MFT (as defined herein above) of that aqueous polymer dispersion with and without the presence of the compound of interest. That is, the MFT of the aqueous polymer dispersion itself is measured. Also, the compound of interest is admixed with the aqueous polymer dispersion, and the MFT of the admixture is measured. If the MFT of the admixture is lower than the MFT of the aqueous polymer dispersion itself, then the compound of interest is suitable as a swelling agent of the present invention.
• suitable swelling agents that are organic compounds
• Some suitable swelling agents are, for example, solvents, surfactants, dispersants, plasticizers, or coalescents.
• Some suitable swelling agents are highly volatile, such as, for example, many solvents.
• Some suitable swelling agents are moderately volatile, such as, for example, coalescents.
• Some suitable swelling agents are only slightly volatile or are nonvolatile, such as, for example, many plasticizers, surfactants, and dispersants.
• the swelling agent includes one or more plasticizers, one or more coalescents, or a mixture thereof.
• Swelling agents suitable in the present invention include, for example, alcohols, ether compounds, carboxylate esters, phosphate esters, amides, and mixtures thereof.
• Some alcohols suitable as swelling agents include, for example, aliphatic alcohols with 2 to 10 carbon atoms. Some suitable alcohols are, for example, isopropanol, butanol, 2-ethylhexanol, and pine oil.
• Some ether compounds suitable as swelling agents are, for example, alkyl and aromatic ethers of monoalkylene glycols and multialkylene glycols, where "multi-" means “di-” or “tri-” or higher; alkylene glycol means a glycol with 2 or 3 or more carbon atoms; and in the case of alkyl ethers, the alkyl group has 1, 2, or more carbon atoms.
• alkyl ethers of multialkylene glycols are, for example, diethylene glycol ethyl ether, dipropylene glycol methyl ether, and mixtures thereof.
• ether compounds suitable as swelling agents are, for example, ether alcohols, which are compounds containing at least one ether link and at least one hydroxyl group.
• ether alcohols are compounds containing at least one ether link and at least one hydroxyl group.
• suitable ether alcohols are, for example, 2-butoxy ethanol and butyl carbitol.
• carboxylate esters which are compounds containing at least one ester link.
• Carboxylate esters are described herein as "esters of" a hydroxyl compound and a carboxylic acid; it is to be understood that such a description refers to the structure of the ester, whether not the ester is made by reacting that hydroxyl compound with that carboxylic acid.
• “Mono-hydroxyl” compound as used herein is a compound with a single hydroxyl group.
• Polyol as used herein is a compound with two or more hydroxyl groups.
• Monocarboxylic acid as used herein is a compound with a single carboxylic acid group.
• Multicarboxylic acid as used herein is a compound with two or more carboxylic acid groups.
• Some carboxylate esters suitable as swelling agents are, for example, esters of mono-hydroxyl compounds and monocarboxylic acids.
• Suitable monocarboxylic acids include, for example, aromatic monocarboxylic acids (such as, for example, benzoic acid) and aliphatic monocarboxylic acids.
• Suitable aliphatic monocarboxylic acids include, for example, alkyl monocarboxylic acids with 4 to 8 carbon atoms.
• Suitable mono-hydroxyl compounds include, for example, mono-hydroxyl alkyl compounds such as, for example, those with straight or branched alkyl groups with 3 to 13 carbon atoms.
• Some further carboxylate esters suitable as swelling agents are, for example, mono- and di-esters of mono-hydroxyl compounds and multicarboxylic acids.
• Suitable multicarboxylic acids include, for example, aromatic multicarboxylic acids (such as, for example, phthalic acid and trimellitic acid) and aliphatic multicarboxylic acids.
• Some suitable aliphatic multicarboxylic acids are, for example, oxalic acid, fumaric acid, maleic acid, adipic acid, and pimelic acid.
• Suitable mono-hydroxyl compounds include, for example, mono-hydroxyl alkyl compounds such as, for example, those with straight or branched alkyl groups with 3 to 13 carbon atoms.
• alkyl and aromatic mono- and di-esters of the glycols described herein above and monocarboxylic acids are also suitable.
• Additional carboxylate esters suitable as swelling agents are, for example, mono-, di- and higher esters of alkyl polyols and monocarboxylic acids.
• Suitable alkyl polyols are those with 4 or more, or 6 or more, or 8 or more, carbon atoms.
• Suitable monocarboxylic acids are, for example, alkyl carboxylic acids with 3 or 4 carbon atoms.
• suitable esters are the following: TexanolTM (from Eastman Chemical), mono- and di-alkyl esters of iso-octane diol, and mono-and di-alkyl esters of butane diol.
• Some phosphate esters suitable as swelling agents are, for example, trialkyl phosphates (such as, for example, tri-2-ethylhexyl phosphate), triaryl phosphates (such as, for example, tricresyl phosphate), and mixed alkyl/aryl phosphates (such as, for example, 2-ethylhexyl diphenyl phosphate).
• trialkyl phosphates such as, for example, tri-2-ethylhexyl phosphate
• triaryl phosphates such as, for example, tricresyl phosphate
• mixed alkyl/aryl phosphates such as, for example, 2-ethylhexyl diphenyl phosphate
• One suitable amide swelling agent is, for example, caprolactam.
• the amount of swelling agent used in the practice of the present invention can be characterized by the weight of swelling agent compared to the weight of the monomer mix.
• the amount of swelling agent is 1 or more parts by weight, or 2 or more parts by weight, or 3 or more parts by weight, or 4 or more parts by weight.
• the amount of swelling agent is 10 or less parts by weight, or 7 or less parts by weight, or 5 or less parts by weight.
• the at least one swelling agent is admixed with the aqueous polymer dispersion, and the result is herein called a "preliminary admixture.”
• the preliminary admixture contains at least 1 part by weight of at least one swelling agent, based on 100 parts by weight of monomer mix.
• the preliminary admixture contains no polyvalent metal cation or contains a relatively small amount of polyvalent metal cation.
• the ratio of equivalents of polyvalent metal cation in the preliminary admixture to equivalents of carboxylic acid functional groups in the preliminary admixture is 0.25 or less. In some embodiments the ratio of equivalents of polyvalent metal cation in the preliminary admixture to equivalents of carboxylic acid functional groups in the preliminary admixture is 0.1 or less, or 0.05 or less; or 0.01 or less.
• the preliminary admixture may be formed by any technique, under any conditions.
• the preliminary admixture may be formed at elevated temperature (higher than 35°C). In other embodiments, the preliminary admixture may be formed at 35°C or lower, or at 30°C or lower.
• the preliminary admixture subsequent to forming the preliminary admixture, is admixed,with at least one polvalent metal cation to form a subsequent admixture.
• the ratio of equivalents of polyvalent metal cation in the subsequent admixture to equivalents of carboxylic acid functional groups in the subsequent admixture is 0.4 or more.
• the ratio of equivalents of polyvalent metal cation in the subsequent admixture to equivalents of carboxylic acid functional groups in the subsequent admixture is 0.5 or more; or 0.6 or more; or 0.7 or more; or 0.8 or more.
• the ratio of equivalents of polyvalent metal cation in the subsequent admixture to equivalents of carboxylic acid functional groups in the subsequent admixture is 1.2 or lower. In some embodiments, the ratio of equivalents of polyvalent metal cation in the subsequent admixture to equivalents of carboxylic acid functional groups in the subsequent admixture is 1.0 or lower, or 0.9 or lower.
• the subsequent admixture may be formed by any technique, under any conditions.
• the subsequent admixture may be formed at elevated temperature (higher than 35°C).
• the subsequent admixture may be formed at 35°C or lower, or at 30°C or lower.
• the subsequent admixture is formed at temperature less than the MFT of the aqueous polymer dispersion.
• the subsequent admixture is formed at temperature approximately equal to the MFT of the aqueous polymer dispersion.
• the subsequent admixture is formed at a temperature above the Tg of the polymer of the aqueous polymer dispersion.
• Tg of the polymer is meant herein the Tg as calculated by the Fox equation (T.G. Fox, Bulletin of the American Physical Society , series II, volume 1, 1956, p. 123), based only on the monomers in the monomer mix and not based on other ingredients admixed with the polymer.
• the subsequent admixture is formed at a temperature equal to or below the Tg of the polymer of the aqueous polymer dispersion, including, for example, embodiments in which the temperature of formation of the subsequent admixture is lower than the Tg of the polymer of the aqueous polymer dispersion by a difference of 4°C or more, or by a difference of 10°C or more.
• the subsequent admixture is formed while the pH of the aqueous polymer dispersion is 7 or less; this condition is contemplated to be useful, for example, when some or all of the polyvalent metal cation is in the form of an insoluble metal compound. In other embodiments, the subsequent admixture is formed while the pH of the aqueous polymer dispersion is higher than 7.
• all or part of the swelling agent and all or part of the polyvalent metal cation are added simultaneously to aqueous polymer dispersion.
• the ingredients may be added at any concentration or feed rate.
• Such a method is considered to be an embodiment of the present invention if, at some point during the simultaneous addition, 1 to 10 parts by weight (based on 100 parts by weight of the monomer mix used to form the aqueous polymer dispersion) of swelling agent is present in the admixture at a time when the ratio of equivalents of polyvalent metal ions in the admixture to equivalents of carboxylic acid functional groups in the admixture is 0.25 or less, and if, in the admixture after the addition of swelling agent and polyvalent metal cation is finished, the ratio of equivalents of polyvalent metal ions in the admixture to equivalents of carboxylic acid functional groups in the admixture is 0.4 or more.
• no further swelling agent is added to the composition.
• some portion of at least one swelling agent for example, one or more plasticizers, one or more coalescents, or one or more of each is added to the composition after the formation of the subsequent admixture.
• the composition of the present invention also includes one or more basic salt of an alkaline metal.
• Basic salts of alkaline metals include, for example, sodium hydroxide, potassium hydroxide, and mixtures thereof.
• the molar ratio of polyvalent metal cation to alkaline metal in the composition is 0.1 to 10.
• small amounts of alkaline metal are present in the composition; in such embodiments, the molar ratio of alkaline metal to polyvalent metal cation in the composition is 0.02 or less; or 0.01 or less; or 0.005 or less.
• no basic salt of an alkaline metal is used.
• the composition of the present invention contains ingredients, known herein as "adjuvants," in addition to those described herein above.
• Adjuvants when present, include, for example, waxes (including, for example, wax emulsions), surfactants, wetting agents, emulsifying agents, dispersing agents, leveling agents, cosolvents, thickeners (including, for example, alkali swellable resins and alkali soluble resins), and mixtures thereof.
• Adjuvants when present, may be added at any point in the formation of the composition of the present invention. Some adjuvants, for example, may be added as part of the process of forming the aqueous polymer dispersion and will remain in the composition.
• Some adjuvants may be added to one or more of the ingredients or to one or more of the admixtures, to improve the properties of the composition.
• Some of these adjuvants may reside in any one of or any combination of the following locations: inside the suspended particles of the aqueous polymer dispersion, on the surface of the suspended particles of the aqueous polymer dispersion, or in the continuous medium.
• one or more amphoteric surfactant is included in the composition. In other embodiments, no amphoteric surfactant is used.
• one or more surfactant is added to the composition after the formation of the aqueous polymer dispersion.
• surfactant is herein called “cosurfactant.”
• Cosurfactant if present, is in addition to any surfactants that may have been used in the production of the aqueous polymer dispersion.
• cosurfactant may be added to the composition of the present invention at any point in the process of forming the composition, including, for example, one of, or any combination of, the following points: cosurfactant may be admixed with aqueous polymer dispersion before aqueous polymer dispersion is admixed with swelling agent; cosurfactant may be admixed with swelling agent before aqueous polymer dispersion is admixed with swelling agent; cosurfactant may be admixed with polyvalent metal cation complex before polyvalent metal cation complex is admixed with preliminary admixture.
• Suitable cosurfactants may be any type of surfactant. Cosurfactants are preferably chosen to be compatible with the aqueous polymer dispersion so as to avoid coagulating or otherwise degrading the aqueous polymer dispersion. Cosurfactants may be cationic, anionic, nonionic, or a mixture thereof. In some embodiments, cosurfactants are nonionic surfactants. Among the nonionic surfactants suitable as cosurfactant are, for example, alkoxylates, sulfates, sulfonates, phosphate esters, copolymers of ethylene oxide and propylene oxide, and mixtures thereof.
• alkoxylates are, for example, ethoxylates, which have the structure R-O-(-CH 2 CH 2 O-) x -H where R is an aliphatic group, an aromatic group, an aliphatic-substituted aromatic group, and aromatic-substituted aliphatic group, or a mixture thereof; and x is from 5 to 200.
• R is alkyl-substituted benzene, with the structure R 1 -R 2 -, where R 1 is a linear alkyl group and R 2 is an aromatic ring.
• One suitable cosurfactant is octylphenol ethoxylate.
• R is an alkyl group, attached to the oxygen atom either at the end carbon or at another carbon. Mixtures of suitable cosurfactants are suitable.
• the amount of cosurfactant can be characterized by the ratio of the solid weight of cosurfactant to the solid weight of swelling agent. In some embodiments, this ratio is 0.05 or more; or 0.1 or more; or 0.2 or more; or 0.4 or more. Independently, in some embodiments, this ratio is 10 or less; or 5 or less; or 2 or less; or 1 or less.
• the polyvalent metal cations and the carboxylic acid functional groups are, in some embodiments, capable of interacting in a way that provides the effect of crosslinking of the polymer.
• the effect of crosslinking can, for example, provide one or more desirable properties to the dried layer of the composition, such as, for example, hardness, durability, other useful properties, or a combination thereof.
• compositions of the present invention are useful for a variety of purposes.
• one or more layers of the composition is applied to a substrate and is dried or allowed to dry.
• such a layer of the composition resides mostly or completely on the surface of the substrate, and the composition is considered a coating.
• the subsequent admixture, optionally further admixed with one or more adjuvants is intended for use as a coating and is known as a coating material.
• one or more layers of the composition of the present invention may be applied to any of a wide variety of substrates including, for example, leather, roofs, and floors.
• a coating material that contains a composition of the present invention is used to coat a floor.
• a coating material is known herein as a "floor polish.”
• Some floor polishes contain one or more adjuvants; common adjuvants in floor polishes include, for example, wax emulsions, alkali soluble resins, wetting agents, emulsifying agents, dispersing agents, defoamers, leveling agents, and mixtures thereof.
• a floor polish contains an aqueous polymer dispersion with average particle diameter of 100 nm or larger, or 130 nm or larger.
• a floor polish contains an aqueous polymer dispersion with average particle diameter 300 nm or smaller; or 200 nm or smaller; or 150 nm or smaller.
• a floor polish contains an aqueous polymer dispersion with average particle diameter 75 nm or larger; or 100 nm or larger.
• a floor polish contains an aqueous polymer dispersion that is made by emulsion polymerization.
• Embodiments of the present invention that are used as part or all of a floor polish include, for example, embodiments in which the Tg of the polymer is 35°C or higher; or 40°C or higher. Independently, in some floor polish embodiments, the Tg of the polymer is 70°C or lower; or 65°C or lower. Independently, in some floor polish embodiments, the Tg of the floor polish formulation (including all ingredients, including polymer, swelling agent, adjuvants if used, etc.) is higher that 25°C.
• ranges of 60 to 120 and 80 to 110 are recited for a particular parameter, it is understood that the ranges of 60 to 110 and 80 to 120 are also contemplated.
• minimum values for a particular parameter of 1, 2, and 3 are recited, and if maximum values of 4 and 5 are recited for that parameter, then it is also understood that the following ranges are all contemplated: 1 to 4, 1 to 5, 2 to 4, 2 to 5, 3 to 4, and 3 to 5.
• An emulsified monomer mixture was prepared by slowly adding the following monomers in sequence to a stirred solution of 117.5 g of a 23% (by weight) solution of sodium dodecylbenzene sulfonate in 2100 g of deionized water: 1980 g butyl acrylate (BA), 2970 g methyl methacrylate (MMA), 3150 g styrene (Sty), and 900 g methacrylic acid (MAA).
• BA butyl acrylate
• MMA 2970 g methyl methacrylate
• Sty 3150 g styrene
• MAA methacrylic acid
• the remaining monomer mixture was gradually fed to the reaction mixture along with a cofeed solution (7.5 g ammonium persulfate, 50 g ammonium bicarbonate, and 340 g deionized water).
• a cofeed solution 7.5 g ammonium persulfate, 50 g ammonium bicarbonate, and 340 g deionized water.
• the rate of addition was chosen so that the temperature remained between 80°C and 84°C.
• the containers and feed lines were rinsed to the reaction vessel, and the contents of the reaction vessel were cooled to 40°C.
• a zinc complex was formed by mixing 368.82 g zinc oxide, 423.15 g ammonium bicarbonate, 423.15 g ammonium hydroxide solution (28% by weight in water), and 1125 g deionized water.
• latex polymers were made from the monomer mixes described in Example 2.
• a variety of admixtures were formed.
• the polymers and swelling agents varied, as shown in the table below.
• the cosurfactant was a nonionic surfactant.
• Each latex polymer that was used is characterized by its "monomer mix" in the table below.
• each latex polymer was stirred at 40°C; cosurfactant (if used) and swelling agent (if used) were gradually added over 20 minutes; and the admixture was then stirred for an additional 10 minutes. With stirring at 40°C, the zinc complex was added gradually over 30 minutes, and the resulting admixture was stirred at 40°C for 10 minutes. The amount of zinc complex added was calculated to give the zinc amount shown in the table below for each example.
• the admixture was cooled to room temperature (approximately 20°C) and filtered through a 325 mesh screen. Then, each admixture was allowed to stand at room temperature (approximately 20°C) overnight. Then each admixture was examined to observe whether any precipitate had formed.
• any precipitate was a zinc compound.
• Example Monomer Mix Cosurfactant amount Swelling agent type swelling agent amount zinc amount precipitate amount 2C A 0 none (9) 0 0.39 large 3C B 0 none (9) 0 0.44 large 4 B 2 caprolactam 2 0.44 light 5 B 2 caprolactam 4.65 0.75 none 6 C 2 note 4 0.90 none
• Floor polishes were made by mixing the following ingredients in the order shown in the following formulation.
• Ingredient Amount kg (lbs) Water 11.81 (26.03) KathonTM CG biocide (1.5% by weight, in water) 0.01 (0.03) RhoplexTM 1531 resin 1.60 (3.53) Ammonia (28% by weight, in water) 0.11 (0.25) MasurfTM FS-230 wetting aid (1% by weight, in water) 0.91 (2.00) Diethylene glycol monoethyl ether 2.04 (4.50) Dipropylene glycol methyl ether 1.13 (2.50) Tributoxy ethyl phosphate 1.47 (3.25) Latex polymer (46.3% by weight, in water) of Example 6 20.92 (46.13) AC-316N wax emulsion (30% by weight, in water) 3.05 (6.72) EpoleneTM E43N wax emulsion 2.28 (5.03) SE-21 0.02 (0.04)
• Example 7 The floor polish of Example 7 was tested. Also tested was a comparative floor polish, which was a commercially available floor polish, which is believed to include a polymer that includes polymerized units of acrylic, methacrylic, and/or styrene monomers and that has carboxylic functional groups; which is believed to include zinc ions; which is believed to be a composition different from the compositions of the present invention, and which is believed to be made by methods different from the methods of the present invention.
• a comparative floor polish which was a commercially available floor polish, which is believed to include a polymer that includes polymerized units of acrylic, methacrylic, and/or styrene monomers and that has carboxylic functional groups; which is believed to include zinc ions; which is believed to be a composition different from the compositions of the present invention, and which is believed to be made by methods different from the methods of the present invention.
• the floor polish of Example 7 is at least as good as the comparative floor polish in every test, and the floor polish of Example 7 is better than the comparative floor polish at Scuff Resistance, Black Mark Resistance, and Soil Resistance.

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